Flavoring with carbomethoxy methyl norbornanes

ABSTRACT

Described are compounds defined according to the generic structure: ##STR1## wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond; and one of R 1  and R 2  is methyl and the other of R 1  and R 2  is hydrogen. In addition, organoleptic uses of such compounds are disclosed for augmenting or enhancing the aroma or taste of consumable materials including foodstuffs, chewing gums, chewing tobaccos, medicinal products, toothpastes, perfumes, perfumed articles (such as liquid or solid, anionic, cationic, nonionic or zwitterionic detergents), fabric softeners and dryer-added fabric softener articles.

This application is a divisional of application for U.S. patent, Ser. No. 284,107 filed on July 16, 1981, now U.S. Pat. No. 4,350,823 issued on Sept. 21, 1982 which is a continuation-in-part of application for U.S. patent, Ser. No. 133,870 filed on Mar. 25, 1980, now U.S. Pat. No. 4,319,036 issued on Mar. 9, 1982. The said patent application Ser. No. 133,870 is herewith incorporated by reference herein.

BACKGROUND OF THE INVENTION

The present invention relates to carbomethoxy methyl norbornanes having the generic formula: ##STR2## wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond; and one of R₁ and R₂ is methyl and the other of R₁ and R₂ is hydrogen, and to novel compositions using one or more of such norbornane derivatives to alter, modify or enhance the flavor and/or aroma of consumable materials or impart flavor and/or aroma to consumable materials.

There has been considerable work performed relating to substances which can be used to impart (modify, augment or enhance) flavors and fragrances to (or in) various consumable materials. These substances are used to diminish the use of natural materials, some of which may be in short supply, and to provide more uniform properties in the finished product.

Application for U.S. patent, Ser. No. 133,870 filed on Mar. 25, 1980 now U.S. Pat. No. 4,319,036 issued on Mar. 9, 1982 relates to compounds generic to the compounds of the instant invention; carboalkoxy alkyl norbornanes having the generic formula: ##STR3## wherein the dashed line represents either a carbon-carbon single or a carbon-carbon double bond; R₁, R₂, R₃ and R₄ represent hydrogen or methyl; with the proviso that one of R₁ or R₂ is methyl and the other of R₁ or R₂ is hydrogen; and with the further proviso that R₃ and R₄ are not both methyl, produced by the novel process of our invention and to novel compositions using one or more of such norbornane derivatives to alter, modify or enhance the flavor and/or aroma of consumable materials or impart flavor and/or aroma to consumable materials.

Mellor and Webb, J. Chem. Soc. Perkin Trans II, 1974 (I) 26-31 discloses production of the compounds having the structures: ##STR4## together with several other methyl substituted isomers thereof in admixture, according to the reaction: ##STR5## The Mellor and Webb article, however, does not disclose the reaction to take place at low temperatures in the presence of an alkyl aluminum halide or dialkyl aluminum halide whereby but two isomers are produced in a controlled fashion in high yields thus yielding an organoleptically acceptable mixture of carboalkoxy norbornane derivatives.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the NMR spectrum for the substance produced according to the reaction of Example I, distillation fraction 5 consisting essentially of the compounds having the structures: ##STR6##

FIG. 2 is the infra-red spectrum for fraction 5 of the distillation product of the reaction product of Example I containing the compounds having the structures: ##STR7##

FIG. 3 is the NMR spectrum for fraction 3 of the distillation product of the reaction product of Example II containing the compounds having the structures: ##STR8##

FIG. 4 is the infra-red spectrum for fraction 3 of the distillation product of the reaction product of Example II containing the compounds having the structures: ##STR9##

THE INVENTION

This invention provides compounds defined according to the generic structure: ##STR10## wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond; and one of R₁ and R₂ is methyl and the other of R₁ and R₂ is hydrogen. This invention also defines organoleptic uses of such compounds in food flavors, chewing gum flavors, medicinal product flavors, toothpaste flavors, fragrances, colognes and perfumed articles, e.g., solid or liquid anionic, cationic, nonionic or zwitterionic detergents.

The compounds defined according to the generic structure: ##STR11## wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond; and one of R₁ and R₂ is methyl and the other of R₁ and R₂ is hydrogen, are specifically defined according to the structures: ##STR12##

The compounds are specifically produced by reacting methyl methacrylate with methyl cyclopentadiene to produce the compounds having the structures: ##STR13## These materials may be used as is and purified as by distillation and preparative chromatography; and/or the materials may be further reacted with a reducing agent such as hydrogen to form additional compounds of our invention defined according to the structures: ##STR14##

Thus, the reactions to produce the compounds of our invention are as follows: ##STR15##

The specific conditions for carrying out the reactions of our invention are set forth in parent application for U.S. patent, Ser. No. 133,870 filed on Mar. 25, 1980 now U.S. Pat. No. 4,319,036 issued on Mar. 9, 1982 and co-pending application, Ser. No. 206,466 filed on Nov. 13, 1980 now U.S. Pat. No. 4,312,888 issued on Jan. 26, 1982. The disclosures of Ser. No. 133,870 filed on Mar. 25, 1980 now U.S. Pat. No. 4,319,036 issued on Mar. 9, 1982 as well as Ser. No. 206,466 filed on Nov. 13, 1980 now U.S. Pat. No. 4,312,888 issued on Jan. 26, 1982 are hereby incorporated by reference to the instant disclosure.

The ranges of utility for their organoleptic properties in consumable materials of the substances of our invention are identical to those ranges set forth in Ser. No. 133,870 filed on Mar. 25, 1980 now U.S. Pat. No. 4,319,036 issued on Mar. 9, 1982 as well as Ser. No. 206,466 filed on Nov. 13, 1980 now U.S. Pat. No. 4,312,888 issued on Jan. 26, 1982.

The organoleptic properties of the compounds of our invention are as follows:

                  TABLE I                                                          ______________________________________                                                        Organoleptic Organoleptic                                       Structure of   Properties   Properties                                         Chemical       in Flavors   in Fragrances                                      ______________________________________                                         Mixture of compounds                                                                          Blueberry, bal-                                                                             A powerful,                                        (as produced according                                                                        samic and piney                                                                             minty, camphor-                                    to Example I) containing                                                                      aroma and taste.                                                                            aceous fruity                                      compounds having the        aroma.                                             structures:                                                                     ##STR16##                                                                     and                                                                             ##STR17##                                                                     Mixture of compounds                                                                          A blueberry, A camphoraceous,                                   (produced according to                                                                        patchouli-like,                                                                             sweaty, menthol-                                   Example II) containing                                                                        camphoraceous                                                                               like aroma with                                    the compounds having the                                                                      aroma with a patchouli-like                                     structures:    blueberry, cam-                                                                             undertones.                                                       phoraceous-like                                                  ##STR18##     flavor profile at 5 ppm.                                        and                                                                             ##STR19##                                                                     ______________________________________                                    

The following examples set forth embodiments of our invention as it is preferred to practice it. The invention is not to be limited thereby but is only limited to the scope of the claims which follow said examples.

EXAMPLE I Preparation of Methyl Ester of 2,5(and 6)Dimethyl-5-Norbornene-2-Carboxylic Acid ##STR20##

Into a 5,000 cc reaction flask equipped with stirrer, condenser, thermometer and dropping funnel and nitrogen blanket apparatus is placed 0.1 moles of ethyl aluminum dichloride and 1,000 cc anhydrous toluene. 460 grams (4.6 moles) of methyl methacrylate is added drop-wise to the reaction mass over a period of 40 minutes while maintaining the temperature thereof at 25°-30° C. Over a period of 1 hour and 15 minutes while maintaining the reaction temperature at 25°-30° C., 800.0 grams (4.6 moles) of methyl cyclopentadiene (46% in toluene) is added to the reaction mass. After addition of the methyl cyclopentadiene, the reaction mass is stirred at room temperature for a period of 45 minutes whereupon the indications are that the reaction has gone to completion. 300 cc of 10% hydrochloric acid is then added to the reaction mass. The reaction mass now exists in two phases; an organic phase and an aqueous phase. The organic phase is washed with two 500 cc portions of 10% sodium bicarbonate and one 300 cc portion of 10% sodium chloride. The reaction mass is then stripped and distilled yielding the following fractions (12" Stone column):

    ______________________________________                                                  Vapor        Liquid                                                   Fraction Temp.        Temp.   Pressure                                         Number   (°C.) (°C.)                                                                           mm/Hg.                                           ______________________________________                                         1        50/55        75/77   3.5/3.0                                          2        55           80      3.0                                              3        55           80      3.0                                              4        55           85      3.0                                              5        55           85      3.0                                              6        55           89      3.0                                              7        55           190     3.5                                              ______________________________________                                    

The reaction mass is then redistilled on an 18" Goodloe packed column yielding the following fractions:

    ______________________________________                                                  Vapor        Liquid                                                   Fraction Temp.        Temp.   Pressure                                         Number   (°C.) (°C.)                                                                           mm/Hg.                                           ______________________________________                                         1        60/60        70/70   3.0/3.0                                          2        60           70      3.0                                              3        60           70      3.5                                              4        55           68      3.0                                              5        55           67      2.8                                              6        54           66      2.0                                              7        54           65      2.5                                              8        55           66      2.5                                              9        55           66      2.5                                              10       55           66      2.5                                              11       55           68      2.5                                              12       54           70      2.5                                              13       54           88      2.0                                              ______________________________________                                    

FIG. 1 is the NMR spectrum for fraction 5 of the foregoing distillation containing the compounds having the structures: ##STR21##

FIG. 2 is the infra-red spectrum for fraction 5 of the foregoing distillation containing the compounds having the structures: ##STR22##

EXAMPLE II Preparation of Methyl Ester of 2,5(and 6)Dimethyl-2-Norbornane Carboxylic Acid ##STR23##

Into a pressure bottle is placed 226.0 grams (1.25 moles) of bulked fractions 2-12 of the distillation product of Example I containing the compounds having the structures: ##STR24## 0.5 grams of 10% palladium on carbon; and 100 cc of anhydrous isopropyl alcohol. The pressure bottle is sealed under nitrogen. Hydrogenation is commenced and carried out over a period of 3.5 hours at which time the hydrogenation ceases. The hydrogenation is carried out at a pressure of 150 psig and at a temperature of 120° C.

At the end of the hydrogenation, the pressure bottle is opened and the reaction mass is filtered and the resulting filtrate is distilled to yield 199 grams (87% of theory). Distillation takes place on a 12" stone packed column yielding the following fractions:

    ______________________________________                                                  Vapor         Liquid                                                  Fraction Temp.         Temp.   Pressure                                        Number   (°C.)  (°C.)                                                                           mm/Hg.                                          ______________________________________                                         1        50/50         70/80   2.5/2.5                                         2        60            80      2.5                                             3        60            80      2.5                                             4        60            180     2.5                                             ______________________________________                                    

The resulting product is then redistilled on an 18" Goodloe column yielding the following fractions:

    ______________________________________                                                  Vapor         Liquid                                                  Fraction Temp.         Temp.   Pressure                                        Number   (°C.)  (°C.)                                                                           mm/Hg.                                          ______________________________________                                         1        55/60         65/70   2.9/2.5                                         2        60            70      2.0                                             3        65            80      2.0                                             4        54            71      1.0                                             5        54            105     1.0                                             6        50            220     1.0                                             ______________________________________                                    

FIG. 3 is the NMR spectrum for fraction 3 of the foregoing distillation containing the compounds having the structures: ##STR25##

FIG. 4 is the infra-red spectrum for fraction 3 of the foregoing distillation containing the compounds having the structures: ##STR26##

EXAMPLE III

The following spicy/woody/minty-type formulae are prepared:

    ______________________________________                                                             Parts by Weight                                            Ingredient            III(A)  III(B)                                           ______________________________________                                         Brazilian mint oil    5.0     5.0                                              Geranium bourbon      15.0    15.0                                             Lavendar oil barreme  10.0    10.0                                             Thyme oil white       10.0    10.0                                             Amyl cinnamic aldehyde                                                                               10.0    10.0                                             Sauge sclaree french  5.0     5.0                                              Sandalwood oil        5.0     5.0                                              Galbanum oil          5.0     5.0                                              Patchouli oil light   5.0     5.0                                              Cedarwood oil light   15.0    15.0                                             Product produced according to                                                                        5.0     --                                               Example I, bulked fractions                                                    2-12 containing and consisting                                                 of the compounds having the                                                    structures:                                                                     ##STR27##                                                                     and                                                                             ##STR28##                                                                     Product prepared according to                                                                        --      5.0                                              Example II, containing bulked                                                  fractions 2-6 containing and                                                   consisting of the compounds                                                    having the structures:                                                          ##STR29##                                                                     and                                                                             ##STR30##                                                                     ______________________________________                                    

When the compositions of matter prepared according to Example I or II are incorporated into the formulae at 5.0%, both compositions of matter add a pleasant minty, woody, camphoraceous, aroma with patchouli-like undertones to the spicy/woody/minty-type perfume formulations.

EXAMPLE IV

A stable lotion is prepared with the following formulations:

    ______________________________________                                         Ingredients           Parts by Weight                                          ______________________________________                                         Poly (N--dimethyl-3,5-dimethyl-                                                                      1.0                                                      ene piperidinium chloride)                                                     (Merquat 100, Merck & Co., U.S.A.,                                             average molecular weight 50,000-                                               100,000 viscosity in 40% aqueous                                               soluiton, 100,000 cps.)                                                        Cocoamidopropyl dimethyl gylcine                                                                     5.7                                                      (betaine)                                                                      Myristyl dimethylamine oxide                                                                         12.0                                                     Stearic monoethanolamide opacifier                                                                   2.0                                                      Perfume material as indicated in                                                                     0.5                                                      Tabel II (below) giving rise to                                                the aroma profiles as indicated                                                in Table II below                                                              Water, color, salts, U.V. absorber                                                                   q.s. to 100                                              ______________________________________                                    

Two or three bottle capfuls of the above lotion held under the tap releasing the water into the bathtub yields a copiously foamed bubble bath with no visible precipitation flocculation, or "bathtub ring" even using hard water. Bathing in this bath is found to have a cleansing and pleasing emollient effect on the skin as described above.

When, after immersion in this bath, the body is soaped, rinsed and dried, an even better, more long-lasting emollient, moisturizing effect on the skin is observed. The foam or bubbles are substantially unaffected by the soaping step, and no precipitate, flocculate or "bathtub ring", or any bothersome film or coating on the bathtub surface is found.

                  TABLE II                                                         ______________________________________                                                            Organoleptic Properties                                     Structure of Chemical                                                                             in Fragrances                                               ______________________________________                                         Mixture of compounds                                                                              A powerful, minty,                                          (as produced according                                                                            camphoraceous, fruity                                       to Example I) containing                                                                          aroma.                                                      compounds having the                                                           structures:                                                                     ##STR31##                                                                     and                                                                             ##STR32##                                                                     Mixture of compounds                                                                              A camphoraceous,                                            (produced according to                                                                            sweaty, menthol-like                                        Example II) containing                                                                            aroma with patchouli-                                       the compounds having the                                                                          like undertones.                                            structures:                                                                     ##STR33##                                                                     and                                                                             ##STR34##                                                                     Perfume composition prepared                                                                      A spicy, woody, minty                                       according to Example III(A).                                                                      aroma profile with                                                             patchouli-like undertones.                                  Perfume composition prepared                                                                      A spicy, woody, minty                                       according to Example III(B).                                                                      aroma profile with                                                             patchouli-like undertones.                                  ______________________________________                                    

EXAMPLE V

The following formulation is prepared with results in properties and use similar to those described in Example IV.

    ______________________________________                                         Ingredients          Parts by Weight                                           ______________________________________                                         "Merquat 100"        1.0                                                       Cocoamidopropyl dimethyl glycine                                                                    8.0                                                       Myristyl dimethyl amine oxide                                                                       16.0                                                      Perfume ingredient as set forth                                                                     0.9                                                       in Table II of Example IV,                                                     supra, giving rise to the aroma                                                profiles as set forth in Table II                                              of Example IV, supra                                                           Water                q.s. 100                                                  ______________________________________                                    

The composition is a clear liquid. Its viscosity may be increased by addition of a lauric or myristic diethanolamide or a soluble polyethylene glycol ester such as polyethylene glycol 6000. In addition, this composition may be rendered opaque by addition of stearic monoethanolamide stearate, polyethylene glycol 600 monostearate or a glyco amido stearate such as "Cerasynt 1P".

EXAMPLE VI

The following shampoo is prepared containing the following ingredients:

    ______________________________________                                         Ingredients           Parts by Weight                                          ______________________________________                                         Tridecyloxy polyethoxy ethanol                                                                       17.3                                                     of ten ethoxy groups                                                           Polyoxyethylene (20) sorbitan                                                                        7.5                                                      monolaurate                                                                    Myristyl dimethylamine oxide                                                                         25.0                                                     (30% active)                                                                   C.sub.10 -C.sub.20 fatty acyl monoethanolamide                                                       2.5                                                      (cocomonoethanolamide)                                                         Polyacrylamide of molecular weight                                                                   0.2                                                      of about 1,500,000                                                             Hydrogen peroxide (30% aqueous                                                                       0.5                                                      solution)                                                                      Perfume ingredient as indicated at                                                                   1.0                                                      Table II of Example IV, supra,                                                 giving rise to the aroma profiles                                              as indicated in Table II of                                                    Example IV, supra                                                              Deionized water (3 micromhos/cm                                                                      46.0                                                     conductivity)                                                                  ______________________________________                                    

A shampoo of the above composition is made in the following matter. First, the tridecyloxy polyethoxy ethanol is addedto a clean mixing tank, with the agitator on, and the amine oxide, polyoxyethylene sorbitan monolaurate and cocomonoethanolamine are added sequentially, with continued agitation. The mix is then heated to 68° C., until the cocomonoethanolamide is melted and/or dissolved. The hydrogen peroxide solution is then admixed with the mentioned nonionics and mixing is continued for about half an hour, in which the peroxide destroys any free amines or other harmful impurities that may be present. The mix is then cooled to 38° C.

In a separate mixer the polyacrylamide is gradually added to the formula weight of deionized water, with the mixer on. Addition is effected carefully and slowly (the polyacrylamide is sprinkled in) to avoid the production of "fish eyes" in the mix. After dissolving of the polyacrylamide the solution thereof is added to the first mixing tank with agitation and is blended with the nonionics, such mixings being at room temperature. Subsequently, the perfume as indicated in Table II of Example IV, supra, giving rise to the aroma profile as set forth in Table II of Example IV, supra, is admixed with the balance of the composition and mixing is continued for another half hour.

The product made is an excellent shampoo of satisfactory viscosity and aroma, foaming power, foam stability, low conductivity and good shampooing effects. The viscosity is about 1,000 centipoises at 20° C. and the conductivity, using the Hach Conductivity Meter, is 750 micromhos/cm. The foaming power is 250 ml and the foam stability is 22 seconds, by the test method previously described. In comparison, a commercial shampoo based on triethanolamine lauryl sulphate detergent has a conductivity of about 22,000 micromhos/cm, a viscosity of about 1,500 centipoises, a foaming power of about 380 ml and a foam stability of 60 seconds.

In panel evaluations of the experimental shampoo compared to a different commercial product, in actual shampooing, the experimental formula was adjudged significantly better in being less drying, producing a softer feel for the wet hair, leaving the wet hair easier to comb, being less prone to accumulate static charges (less flyaway) and having a foam of better appearance and feel. Additionally, the experimental product was judged better in almost all hair effect properties, with the control only being about equal to it in curl retention. In properties other than those mentioned the experimental product was better in rinsability, the control was better in foam build-up rate and the foams were about equal in volume and stability.

In the shampooing described herein and in subsequent Examples the human hair is washed on the head by wetting the hair with warm tap water at about 42° C., applying 15 grams of shampoo to the hair, lathering it into the hair for a minute, rinsing with warm tap water for 30 seconds, re-lathering with 7 grams of shampoo for a minute and rinsing off for 30 seconds, after which the hair is towel dried and dried further with an automatic hair dryer.

EXAMPLE VII Fabric Freshener Composition

A fabric freshener composition is prepared as follows:

    ______________________________________                                         Ingredients        Parts by Weight                                             ______________________________________                                         Sodium bicarbonate 3                                                           "Kyro" EOB (Trademark)*                                                                           1                                                           Perfume ingredient as set                                                                         1                                                           forth in Table II of                                                           Example IV, supra, giving                                                      rise to an aroma as set                                                        forth in Table II of                                                           Example IV, supra                                                              Water              0.05                                                        ______________________________________                                          *A commercial nonionic surfactant comprising an average of eleven carbon       atoms, ethoxylated to an average of 9 ethyleneoxy groups per molecule.   

The composition of this Example is prepared by simply mixing the ingredients.

The above described composition is applied to a lightly soiled and wrinkled fabric as droplets (ca. 5.0 mm avg. size) using a trigger action sprayer having a nozzle which is adjustable to provide composition droplets in the desired range. The composition is applied at a rate of about 1 gram of composition to about 10 grams of fabric.

The fabric is then placed in an automatic dryer and dried, with tumbling action, at a temperature of 60° C.-80° C. for a period of 15 minutes. The fabric is rendered free of wrinkles and static, and has a fresh appearance and pleasant odor profile as set forth in Table II of Example IV, supra. Surprisingly, the sodium bicarbonate is not visible on the refreshed fabric.

In the foregoing procedure, substantially the same results were obtained when sodium carbonate is substituted for the sodium bicarbonate.

EXAMPLE VIII Perfumed Liquid Detergent

Concentrated liquid detergents (lysine salts of n-dodecyl benzene sulfonic acid as more specifically described in U.S. Pat. No. 3,948,818, issued on Apr. 6, 1976) with aromas as indicated in Table II of Example IV, supra, are prepared containing 0.10%, 0.15%, 0.20%, 0.25%, 0.30%, 0.40%, 0.50% and 0.80% of the perfume ingredient as set forth in Table II of Example IV, supra. The detergents are prepared by adding and homogeneously mixing the appropriate quantity of perfume ingredient as set forth in Table II of Example IV, supra. The detergents all possess aromas as set forth in Table II of Example IV, supra with the intensity of each increasing with greater concentrations of the perfume ingredient as indicated in Table II of Example IV, supra.

EXAMPLE IX Preparation of a Cologne and Handkerchief Perfume

The perfume ingredient as set forth in Table II of Example IV, supra, is incorporated into colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 5.0% and 6.0% in 75%, 80%, 85%, 90% and 95% aqueous ethanol solutions. Distinct and definite aromas as set forth in Table II of Example IV, supra, are imparted to the colognes. The perfume ingredients as indicated in Table II of Example IV, supra are also added to handkerchief perfumes at concentrations of 15%, 20%, 25%, 30% and 35% (in 75%, 80%, 85%, 90% and 95% aqueous ethanol) and aroma profiles as set forth in Table II of Example IV, supra are imparted to the handkerchief perfume.

EXAMPLE X Blueberry Flavor Formulation

The following formulation is prepared:

    ______________________________________                                         Ingredients         Parts by Weight                                            ______________________________________                                         Heliotropin         3.0                                                        Terpinenol-4 (10% in 95%                                                                           0.2                                                        aqueous food grade ethanol)                                                    Benzaldehyde        1.5                                                        Anisaldehyde        0.2                                                        Phenyl acetaldehyde 0.4                                                        Benzyl formate      0.5                                                        Benzyl acetate      2.0                                                        Cis-3-hexenyl benzoate (10%                                                                        0.5                                                        in 95% aqueous food grade                                                      ethanol)                                                                       Methyl hexanoate    2.0                                                        Hexanal             1.0                                                        Eucalyptol (1% in 95% aqueous                                                                      0.5                                                        food grade ethanol)                                                            Eugenol             0.2                                                        Acetaldehyde        3.0                                                        Ethyl acetate       21.0                                                       Ethyl butyrate      26.0                                                       Propylene glycol    38.0                                                                           100.0                                                      ______________________________________                                    

The above formulation is split into 5 portions. To the first four portions are added at the rate of 1%, the norbornane derivatives of Table I, supra. To the fifth portion, nothing is added. All five formulations with and without said norbornyl derivatives are combined with water at the rate of 100 ppm. The flavor of the first four portions each including a norbornyl derivative prepared according to the preceding examples as indicated in Table I, supra, have fruity, blueberry characteristics with several other nuances as indicated in Table I, supra, and are all closely similar to the flavor of wild blueberries. It is therefore preferred to use the formulations containing the norbornyl derivatives as listed in Table I, supra, to the basic blueberry formulation which does not contain any of said norbornyl derivatives.

EXAMPLE XI Fruited Tapioca Cream

The contents of Ann Page Tapioca pudding mix (ingredients: sugar, corn starch, tapioca, sodium chloride, tapioca flavor and artificial color; net weight 138 grams) is emptied into a sauce pan. Three cups of milk are added together with one beaten egg yolk previously blended therewith. The resulting mix is cooked over medium heat stirring constantly while slowly adding at the rate of 0.2%, either one of the flavor materials of Example X (blueberry flavor) each of the materials containing one of the norbornyl derivatives of Table I, supra. The resulting mixture after heating, is then cooled to room temperature in the saucepan. One egg white is slowly added to the resulting mixture together with three tablespoons of sugar. The resulting mixture is then blended and chilled yielding pleasantly tasting blueberry tapioca cream desserts depending upon whether the materials of Example X are added.

EXAMPLE XII Flavored Instant Pudding

A pudding mix (Royal Instant, net weight 3.5 ozs. produced by Standard Brands, Inc., New York, N.Y. 10022) is intimately admixed with 2 cups of cold fresh whole milk. To this mixture, at the rate of 0.3%, is added one of the blueberry flavors of Example X containing the norbornyl derivatives as listed in Table I, supra. The resulting mixture is blended in a Waring blender for a period of three minutes. The resulting mixture is then cooled at 15° C. for a period of five minutes. The resulting puddings have excellent natural blueberry flavors.

EXAMPLE XIII A. Powder Flavor Composition

20 grams of the flavor composition of Example X (containing at least one of the norbornyl derivatives of Table I, supra) is emulsified in a solution containing 300 grams gum acacia and 700 grams water. The emulsion is spray-dried with a Bowen Lab Model Drier utilizing 260 c.f.m. of air with an inlet temperature of 500° F., an outlet temperature of 200° F., and a wheel speed of 50,000 rpm.

B. Sustained Release Flavor

The following mixture is prepared:

    ______________________________________                                         Ingredients        Parts by Weight                                             ______________________________________                                         Liquid blueberry flavor                                                                           20                                                          composition of Example X                                                       Propylene glycol   9                                                           Cab-O-Sil® M-5 (brand of                                                                      5                                                           Silica produced by the                                                         Cabot Corp. of 125 High St.                                                    Boston, Mass. 02110;                                                           Physical properties:                                                           Surface area: 200 m.sup.2 /gm                                                  Nominal particle size: 0.012                                                   microns                                                                        Density: 2.3 lbs./cu. ft.                                                      ______________________________________                                    

The Cab-O-Sil® is dispersed in the liquid blueberry flavor composition (containing the norbornyl derivatives of Table I, supra) of Example X with vigorous stirring, thereby resulting in a viscous liquid. 71 parts by weight of the powder flavor composition of Part A, supra, is then blended into the said viscous liquid, with stirring, at 25° C. for a period of 30 minutes resulting in a dry, free-flowing sustained release flavor powder.

EXAMPLE XIV

10 parts by weight of 50 Bloom pigskin gelatin is added to 90 parts by weight of water at a temperature of 150° F. The mixture is agitated until the gelatin is completely dissolved and the solution is cooled to 120° F. 20 parts by weight of the liquid flavor composition of Example X (containing at least one of the norbornyl derivatives of Table I, supra) is added to the solution which is then homogenized to form an emulsion having particle size typically in the range of 2-5 microns. This material is kept at 120° F. under which conditions the gelatin will not jell.

Coacervation is induced by adding, slowly and uniformly, 40 parts by weight of a 20% aqueous solution of sodium sulfate. During coacervation, the gelatin molecules are deposited uniformly about each oil droplet as a nucleus.

Gelatin is effected by pouring the heated coacervate mixture into 1,000 parts by weight of 7% aqueous solution of sodium sulfate at 65° F. The resulting jelled coacervate may be filtered and washed with water at temperatures below the melting point of gelatin, to remove the salt.

Hardening of the filtered cake, in this example, is effected by washing with 200 parts by weight of 37% solution of formaldehyde in water. The cake is then washed to remove residual formaldehyde.

EXAMPLE XV

100 parts by weight of chicle are mixed with 4 parts by weight of the flavor prepared in accordance with Example XIII. 300 parts of sucrose and 100 parts of corn syrup are added. Mixing is effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inch in width and 0.1 inches in thickness. The strips are cut into lengths of 3 inches each. On chewing, the chewing gum has a pleasant, long-lasting blueberry flavor.

EXAMPLE XVI Chewing Gum

100 parts by weight of chicle are mixed with 18 parts by weight of the flavor prepared in accordance with Example XIV. 300 parts of sucrose and 100 parts of corn syrup are then added. Mixing is effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co.

The resulting chewing gum blend is then manufactured into strips 1 inch in width and 0.1 inches in thickness. The strips are cut into lengths of 3 inches each. On chewing, the chewing gum has a pleasant, long-lasting blueberry flavor.

EXAMPLE XVII Toothpaste Formulation

The following separate groups of ingredients are prepared:

    ______________________________________                                         Parts by Weight                                                                               Ingredients                                                     ______________________________________                                         Group "A"                                                                      30.200             Glycerine                                                   15.325             Distilled water                                             .100               Sodium benzoate                                             .125               Saccharin sodium                                            .400               Stannous fluoride                                           Group "B"                                                                      12.500             Calcium carbonate                                           37.200             Dicalsium phosphate (dihydrate)                             Group "C"                                                                      2.000              Sodium N--lauroyl sarcosinate                                                  (foaming agent)                                             Group "D"                                                                      1.200              Flavor material of Example                                                     XIII (B)                                                    100.000   total                                                                ______________________________________                                    

Procedure

1. The ingredients in Group "A" are stirred and heated in a steam jacketed kettle to 160° F.

2. Stirring is continued for an additional three to five minutes to form a homogeneous gel.

3. The powders of Group "B" are added to the gel, while mixing, until a homogeneous paste is formed.

4. With stirring, the flavor of "D" is added and lastly the sodium n-lauroyl sarcosinate.

5. The resultant slurry is then blended for one hour. The completed paste is then transferred to a three roller mill and then homogenized, and finally tubed.

The resulting toothpaste, when used in a normal toothbrushing procedure, yields a pleasant blueberry flavor, of constant strong intensity throughout said procedure (1-1.5 minutes).

EXAMPLE XVIII Chewable Vitamin Tablets

The flavor material of Example XIII(B) (containing norbornyl derivatives of Table I, supra) is added to a chewable vitamin tablet formulation at the rate of 10 gm/Kg which chewable vitamin tablet formulation is prepared as follows:

In a Hobart Mixer, the following materials are blended to homogeneity:

    ______________________________________                                                            Gms/1000 Tablets                                            ______________________________________                                         Vitamin C (ascorbic acid) as                                                                        70.00                                                     ascorbic acid-sodium ascorbate                                                 mixture 1:1                                                                    Vitamin B.sub.1 (thiamine mononitrate                                                               4.0                                                       331/3% (Hoffman La Roche)                                                      Vitamin B.sub.2 (roboflavin) as Rocoat®                                                         5.0                                                       roboflavin 331/3%                                                              Vitamin B.sub.6 (pyridoxine hydrochloride)                                                          4.0                                                       as Rocoat® pyridoxine hydrochloride                                        331/3%                                                                         Niacinamide as Rocoat® niacinamide                                                              33.0                                                      331/3%                                                                         Calcium pantothenate 11.5                                                      Vitamin B.sub.12 (cyanocobalamin) as                                                                3.5                                                       Merck 0.1% in gelatin                                                          Vitamin E (dl-alpha tocopheryl                                                                      6.6                                                       acetate) as dry Vitamin E acetate                                              331/3% Roche                                                                   d-Biotin             0.044                                                     Flavor of Example XIII(B) containing                                                                (as indicated above)                                      norbornyl derivatives of Table I,                                              supra                                                                          Certified lake color 5.0                                                       Sweetener - sodium saccharin                                                                        1.0                                                       Magnesium stearate lubricant                                                                        10.0                                                      Mannitol q.s. to make                                                                               500.0                                                     ______________________________________                                    

Preliminary tablets are prepared by slugging with flat-faced punches and grinding the slugs to 14 mesh. 13.5 grams dry Vitamin A acetate and 0.6 grams Vitamin D are then added as beadlets. The entire blend is then compressed using concave punches at 0.5 grams each.

Chewing of the resultant tablets yields a pleasant long lasting, consistently strong blueberry flavor for a period of 12 minutes. 

What is claimed is:
 1. A process for augmenting or enhancing the blueberry aroma or taste of a consumable material selected from the group consisting of foodstuffs, chewing gums and toothpastes comprising the step of adding to a foodstuff, chewing gum or toothpaste base, a blueberry aroma or taste augmenting or enhancing quantity of a mixture of two norbornyl derivatives defined according to the structure: ##STR35## wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond and one of R₁ or R₂ is methyl and the other of R₁ or R₂ is hydrogen, wherein in the mixture, the dashed lines are the same.
 2. The process of claim 1 wherein the consumable material is a foodstuff.
 3. The process of claim 1 wherein the consumable material is a chewing gum.
 4. The process of claim 1 wherein the consumable material is a toothpaste. 